Anthraquinone dyestuffs and process for their manufacture



Patented June 28, 19 38 VANTHRAQUIINONEQDYESTUFFS AND moo; l ESSFOR THEIR MANUFACTURE Albin Peter, Basel, Switzerland, assignor to the firm Chemical 'Switzerland Works, formerly Sandoz, Basel,

' 1 51Drawing. A lication'Marh 13,- 1935. se-

rial No. 10,938. In Germany March 21, 1934 I s Claims. (01. 260-60), ,1 I

configurationis generally carried out in presence The present invention relates tonew anthraquinone dyestufi's and to aprocess for 'their manufacture.

It has been found that new valuable dyestuffs of the anthraquinone series can bepreparedby condensing aromatic amines of the general formula wherein X and Y represent alkyl and halogen and Z represents hydrogen, alkyl, halogen or alkoxy, 'With such anthraquinone compounds that contain at least one group replaceable by an aromatic amine. a

'The aromatic amines useful for the production of the new anthraquinone dyestuffs are for example 1,-amino-2,4,6-trimethylbenzene, l-amino- 2,6-dimethylbenzene; 1-amino-2,4-dimethyl- 6 bromobenzene, l-amino-6 -ethyl-2,4-dimethylbenzene or the like.

As anthraquinone compounds which can, be used in the present process, the following maybe listed:

The alphaaminoanthraquinones, their homologues and derivatives, halogenated in an (at-position, such as l-amino-4-bromo-anthraquinone, 1 amino-4-chloroanthraquinone, l amino 2- methyl-4-bromo-anthraquinone, l-amino-2-sulpho-4-bromo-anthraquinone,. 1-methylamino-4- bromo-anthraquinone, 1-amino-2,5-disulphoor 2,8-disulpho-4-bromo=anthraquinone, l-amino- Z-ca'rboxy--bromo-anthraquinone, l amino 2'- cyano-4-bromo-anthraduinone, l-amino-5 -chloro-anthraquinone, 1-amino-2-methoxy-,4-bromoanthraquinone, l amino 2-phenoxy-4-bromo-' quinone, 1-amino-2,4-dibromo-5-chloro-anthraof a solvent and a catalyst, at temperatures between 50 and 250 0., and in an open or in a closed vessel. As suitable-solvents the following,

or mixtures thereof, can be used: water, ethanol, 1 methanol, chlorobenzene, nitrobenzene, dimethylaniline, phenol, glacial acetic'acid and the 0,0- disubstituted aromatic bases themselves, when they are used in excess. I

7 As catalyst generally copper salts: are. used, but it is alsopossible to carry out the condensation in absence of copper.

, Sometimes it is advantageous to carryout the condensation in an inert atmosphere, for exam ple in nitrogen or carbon dioxide atmosphere,

preferably under addition to the reaction mixture sulphonated, valuable compounds for the dyeing of lacquers, like nitrocellulose lacquers, or of cellulose esters and ethers.

If it is intended to obtain water-soluble dyestufis,j the condensation products obtained as above described are subjected to, a sulphonation process, whichmay be carried outby different methods. If the condensation products contain in their moleculea group that can be replaced by the sulphonic acid group, as isthe case in the p-halogen derivatives, then they are transformed into water-soluble dyestuffs by heating them with sulphites, whereby the halogen becomes replaced by the sulphonic acid group. 3

But it is possible to prepare .water soluble dyestuffs from water-insoluble condensation products by sulphonating 'them with sulphuric acid or fuming sulphuricacid of an appropriate. concentration of S03 or with chlorosulphonic acid, whereby one or more sulphonic acid groups .will be introduced into thearyl or into the anthraquinone nucleus. It isfalsopossible to combine both sulphonation methods, that is the direct sulphonation in the aryl nucleus and the subsequent introduction of sulphonic acid group by the sulphite method. These sulphonation methods are well known in the art and canbe carried out in the usual manner.

By subjecting the sulphonated or unsulphonated condensation products containing a free 7 p-po'sition to the imino group in the aryl radical to theaction of aldehydes such as formaldehyde, acetaldehyde, benzaldehyde, benzaldehyde-dirsulphonic acid etc. in an acid or neutral medium, diand triarylmethane derivativescan be produced. By treating the above mentioned compounds with oxidizing agents such as nitric acid', peroxideof manganese and the like, they yield valuable diaryl derivatives of theanthraquinone with very pure and brilliantshadeszand iof ex.

cellent fastness properties. v u

One object of the present invention is there fore, theanthraquinone dyestuffs containing in thir'smolecule at least'o'ne group wh r X nd represent halon e ndja kvl, Y represents hydrogen and a sulphogroup -and Z represents hydrogen, halogen, alkyl and alkoxy.

'sulpho and a linkage binding two of such group -CI- I phenyl and by ordinary linkage between 7 the G-atoms offboth nuclei. V H

Another object of the present invention is the process for the manufactureoi anthraguinone 'dyestuifs, consisting in condensing V anthr'aquinone derivatives, with .the above listed o,o,di-

7 Still another object of the present invention is the'process ior'thecondensation of the anthraquinone derivatives with, the QOp-disubstituted aromatic amines of the benzene series, consisting in that the condensation is carriedoutin presence of solvents or diluents and catalysts, such as copper or copper salts, and inpresence of acid-binding agents and at temperatures between and 250 C.

Still another objectoithe presentinvention, is the condensation process, wherein as acid-' binding agents an excessof the.o,o-disubstituted .aromatic amines of ,thejbenzene series is used.

Still another object of the presentinvention is the process of transforming .the water-insoluble condensation products of anthraquinone derivatives with the o ,o-d i substituted aromatic amines into water-soluble dyestuffs, by treating them with sulphonating agentasuch as sulphuric acid or fuming sulphuric acid or sulphites. 7

7 Still another object of the present invention is the process .of transforming the condensation productsof the anthraquinone series into corresponding anthrapyridones or anthrapyrimidones by treating them with esters. of aceto-acetic or malonic acids or with amides of carbonic acid.

Still another object of the present invention is the process for transforming the-condensation products of the anthraquinone' series obtained as above described into diphenyl-compounds or into diphenyland.triphenylmethane-compounds of the anthraquinone series, .by treating such condensation products that contain a free p position to theimino groupin the nucleus of the o,o-disubstituted aromatic base, with oxidizing agents or with aliphatic or with aromatic aldehydes. r 1 The following examples, without being limita- "tive, illustrate the present invention, the parts being by weight.

Example 1;

10 parts of C;carbethoziy-Z-methybfl-bromoanthrapyridone are heated half an hour to amino- 2,456-trimethylbenzene, 4 parts of potas- -15 Q-160 C. under stirring with 30 parts of 1- si-urnacetate and 0: 1 part of copper powder.

After the'condensation is terminated, the reactionmass'is allowed' to cool down to about 100' dilutedwith 50 parts of ethanol and allowed to'crystallizei Theprecipitate thereby obtained is filtered, washe d firstwith ethanol and there- "on with water .andidried.

The intermediate product obtained. in this manner. isathen sulphonated with weak oleum at a o t 0 Q-a d the i l h na n mx urerzm on ice. The soluble dyestuff thereby obtained is then isolated in the usual manner. It dyeswool a. brilliant. .red ylellow shade of excellent fast ness to milling and. to perspiration; It possesses the formula CH3 7 A dyestufi of similar shade can be obtained if substituted aromatic am'ines-ofthe benzene series. 1amino'zAstnimethylbenzene "is replaced by an; equivalent .quantit y, of l-Qamino-ZA-dimethyl-fi-bromobenzene. r

20 parts of bl-methyl-el-brorno-anthrapyridone, 8 parts of potassium acetate',;0.1 part of copper powder and "70 parts of 1-amino-2,6-di- 'methylbenzene are heated up to 1'50-160 C,, until the condensation is finished, what generally occurs after 2 to 3 hours. The reaction mixture is then allowed to cool down, diluted with 100 parts of methanol and the precipitated base separated by filtration. v The product thereby obtained is then sulpho ,nated with weakoleum and the dyestuff thereby obtained isolated in the usual -manner. It dyes animal, fibres scarlet shades of excellentfastnesses and possesses the formula V .C a V Example 3 pyrimidone will be obtained, which on sulphonaas acid dyestufi which dyes wool'brilliarit 'reddish-blue shades with good properties.) i i The dyestuff thus obtained possesses the for.-

mula

. anti-10H; I 2

,By treating the basefaboveobtainedwith urea in presence of phenol 'assolvent, an anthra tion yields a water-soluble dyestuff dyeing wool bluish-red shades. 1

In the same manner'dyestuffs from 1 hydroxy-4 bromo-anthraquinone and 1-amino-.2,6- dimethylbenzene or other 0,0-disubstituted aromatic amines can be prepared.

Example 4 10 parts of l-amino-2-methyl-4 -bromo-anthraquinone, parts of 1-amino-2,4,6-trimethylbenzene, 4 partsof potassium acetate and 0.1

part of copper powder'are heated up to 150-160 .C., until the condensation is complete and the base thereby produced is then isolated as above described. On sulphonation of the base with oleum, a dyestuff is obtained dyeing wool' level and brilliant violet-blue shades of excellent fastness to light and milling. Thedyestuff possesses the formula NR2 I i a By 'sulphonating the base with'weak oleum at 40 C. a dyestuif is obtained which dyes wool.

brilliant reddish-blue shades of excellent fastness to light, milling, perspiration-and chromirre.

Its formula is:

. CH: CO 803K By replacing the 1-amino-2,6-dimethylbenzene by 1-amino-2,4,6-trimethylbenzene, a similar dyestuff will be obtained.

By using 1,5-dichloro-anthraquinone instead of the 1,4-compound, a red dyestuff will be obtained, which gives on wool dyeings of very good fastness to milling and'to light.

7 Example 6 2 01p arts of glacial aceticjacid, 22 parts of a concentrated aqueoussolution of ammonium hydroxid e, 40 parts "of water, 20 parts of l-amino- -2,4-dibromoanthraquinone, 0.2 part of copper powder and parts of l-amino-2,6-dimethylbenzene are heated on a reflux during 24 hours.

On dilution with 100 parts of ethanol, the base precipitates in form of violet needles and is iso-.

lpart of this base isv heated with 2 parts of an aqueous solution of potassium sulphite (50%) and 4 parts of phenol during 16.hours at C.

and after this time phenol is-separated from the reaction mixture by blowing it out by meansof water steam. The solution thus remaining is then filtered and the dyestufi is salted out.-

The dyestuff dyes; animal fibres a brilliantreddish-blue shade and possessesthe formula these dyestuffs with sulphuric acid or oleum, new

dyestuffs containing two sulpho groups will be obtained. They are easier soluble in water, give redder shades and can be used for printing purposes Example 7 parts of water, 50 parts of ethanol, 20 parts of the sodium salt of l-amino-l-bromo-anthraquinone-Z-sulphonic acid, 10 parts of sodium bicarbonate, 02 part of copper powder and 40 parts of 1-amino-2,6-dimethylbenzene are heated together during 10 hours on a boiling water bath. The ethanol and the excess of the aromatic base are thereupon driven 01f by means of water steam and the dyestuff obtained is precipitated by means of an addition of salt. It is identical with the dyestuff prepared'asdescribed in Example 6.

15 parts of this dyestufi are dissolved in parts of sulphuric acid of 93% and partially precipitated by addition of 65 parts of water. To the suspension thus obtained there are added 1.6 parts of a formaldehyde solution of 40% and the mixture is heated for three hours at 80 C. After this time, a test shaken with cold water shows that the dyestuff has become insoluble. The

- crystalline suspension is then filtered, the precipitate is mixed with a small quantity of water, neutralized with hydroxide of sodium or potassium, filtered and dried. The dyestuff thus obtained dyes wool or natural silk from an acid or neutral dye bath brilliant reddish-blue shades. The wool dyeings possess excellent fastness to milling, washing, potting and to light.

This dyestuff has the following formula:

NH: NHz

HOaS- a 'diphenyl derivative of the formula Instead of treating the sulphuric acid solution of the dyestuff with formaldehyde, it is possible to treat it with peroxide of manganese, whereby will be obtained. This dyestuff possessessimilar properties to those of the.diphenylrnethane compound, prepared as above described.

Example 8 on a mixture of ice and sodium chloride solution,

and the precipitate thereby obtained is filtered and washed until it has become neutral. The moist paste is then mixed with BO-parts of an aqueous solution of potassium sulphite (50%) and 60 parts of phenol and heated in an autoclave for 16 hours at C. After elimination of phenol by means of distillation with water steam, the solution is filtered and the dyestuif salted out. The dyestuff thereby obtained possesses the formula: N112 on oo 3 sonar HN- E;-CH3

and dyes wool pure blue shades of good proper;

ties to washing.

By using as aromatic base the l-amino-2,4,6-, trimethylbenzene a dyestuff possessing a pure but a little redder shade will be obtained.

Example 9 20 parts of the sodium salt of 1-amino-2,4- dibromo-anthraquinone 5-sulphonic acid, 5 parts of sodium bicarbonate, 0.2 part of copper powder, 150 parts of water, 50 parts of ethanol and 20 parts of 1-amino-2,4,6-trimethylbenzene are heated on a reflux during 20 hours. The reaction mixture is then distilled with Water steam in order to drive oil the ethanol and the excess of the aromatic base, and the difiicultly soluble dyestuff separated by filtration and washed with salt Water.

This dyestufi still in moist state is then mixed" with 20 parts of an agueous solution of potassium sulphite and 50 parts of water and heated under pressure during 16 hours at C. Af-

' bromoaanthraquinone-2,8-disulphonic aldehyde disulphonic acid, and the reaction mix- .ter .this'time it-has been transformed into ;a better solubledyestufi of the formula 7 NHg 1 1. (I333 1 s -Q i- OH.

dyeing wool pure blue shades of excellent fastness properties. Thisdyestuff can also be used in the printingindustryas.it,possesses a very good solubility. 7 As' starting product it is also possible-to use the sodium salt of l-amino-Zflwdibromo-anthraquihone-8sulphonic vacid or the mixture of the isomers sulphonated in the 5- and 8-position.

7 Similar easily water-soluble blue dyestufls are 9 obtained by usingthesodium salts 'of leamino- 2,4-dibromo-anthraquinone-6- or 7-sulphonic acid or the mixture of both'isomers.

Example 10 20 parts of atechnical mixture containing the potassium salts of. .l amino--bromo-anthraquinone-2,5- disulphonic acid and l-amino-4- acid, 5 parts .of sodium bicarbonate, 0.2 part of copper powder, parts of water, 50 parts of ethanol and 20 parts of l-amino2,4,6-trimethylbenzene are heated, on a reflux during 24 hours and the dyestufi thereby formed is precipitated by .an addition of hydrochloric, acid. The precipitate is then filtered and worked up in the usual manner.

It dyes wool blue shades of good jiastness properties. 1

Example '11 20 parts of l-amino-2 sulpho-4-bromo-anthraquinone, 10 parts of sodium bi-carbonate, 0.2 part of copper powder, 50 parts of ethanol, 20 parts of 1-amino-2,4,6-trimethylbenzene and 150 parts of Water are heated together under stirring at 70 C. until the formation of the dyestufi has occurred. Ethanol and the excess of the aromatic base are thereupon distilled off with water steam, and the dyestuff, which precipitates thereby in crystallized form, is filtered. By dissolving .it in Water and acidulating itsaqueous solution with sulphuric acid, it can be precipitated in pure form.- It dyes wool brilliant well levelling blue shades of excellent fastness to washing and to light and possesses the formula:

7 CH3 Example 12 14 parts of the dyestufi prepared according to Example 3 from 1methylamino-4-bromoanthraquinone and l-amino-2,6-dimethylbenzene are dissolved in parts of concentrated sulphuric acid and precipitated by means of an addition of 57 parts of water. The suspension is then stirred first for several hours at normal temperature, then for 2 hours at 40-60 C. with 7.5 parts of the crystallized sodium salt of benzv V $2,121,928 I .ture poured into 5001: partsofwatei. The pre- Eaiampi 7 cipitate therebyobtained isfiltered, suspended in i v 1000 parts of water heated to the boil and filtered C =acetyl-2,4 dibromo-anthrapyridone is con- -.from' some of the unreacted starting product? 'densed with 1-amino-2,6-dimethylbenzene in the The dyestuff is then salted out and isolated by manner described in Example land the base 5" filtration.- It is soluble in water with a blue thereby obtained, transformedinto the 2-sulcoloration and dyes wool vfro'man acidbath blue 7 phonic acid derivative byheatingit with a con 7 shades of 'good fa stness to milling to per- I centrated potassium sulphite solution and phenol spiration. Its formula is: I for 16 hours at 140 C.

"'IIIH-CHP OHa-HN' NH-- (ll-- on? s0'3n cm I V20; p a v 20 n I 4= parts of the dyestufi thereby obtained are 6 3 dissolved in 35- parts of concentrated sulphuric ,n E v 2 acid'andthe'solution iscooled"d0vvn to '6 C. r In a similar manner it is possible to transform At this temperature are slowly added 0.6 part of 25 thefcondensation product obtained according to peroxide of manganese of'70%. The temperature Example 4 {from I 1 --amino-2-inethyl4-bromois then allowed to .rise up to 0 C. and the reacanthraquinone and l-amino-2,6-dimethylbenzene tion'rnixtu're is allowed to stand overnight at into. a -vvater-sol11b1e violetmdyestufigiofr the .'ordinary temperature. The reaction mixture is:

formula:. w

' .-then heated for a short time at 40 C. and poured- 1 -v f VCOY, I O0 7 OH: I i 7 70H:- :;l

co vli I v i f I Q 7 w 40 a: n F -'-so,H a v 1 "'40 I into coldwater, whereby the produced dy'stufi y'precipitates. The dyestuff is separatedby filtra- V p I tion, redissolved in water, neutralized 'and'salted som 7 I g 453 I I ,'The new dyestuff dissolves in vvater with bluev mp 13 o 0 red coloration and'dyes wool blue red tints of n V l0 parts oithe condensation product obtained; good fastness to light and to milling. 'Its formula according to Example 6 from 1-amino-2,4-di-. is: bromo-anthraquinone and 1-amino-2,6-dimethy1-;2 i benzene are dissolved in 60 parts of sulphuric I acid of 80% and heated during 4 hours at 60 C. and under good stirring with 4.5 parts of the H sodium salt of benzaldehyde disulphonic acid I o. (cryst.) The reaction Lmixture isthe'reupon: 5: poured into 500 parts of water, the precipitated 1 5 dyestufi "separated by filtration, redissolve d in 4 water, neutralized and salted out. The dyestufi 'ther'eby obtained dyes wool blue violet shades of 7 very good fastness properties and possesses the 1 a V formulaz 7 v J I i x -15 'WhatIclaimist.

thraquinone compounds containing inan u-position at least one-member of the group consist} ing of halogen, nitro, alkoxyand hydroxy with quinone dyestuffs, comprising condensing sulan aromatic amine of the general formula 1 consisting of hydrogenandmethyl,

wherein X stands fora member of the'groupc'on sisting of methyl and, ethyl;Y ,-stands foria-mem-ij ber oftheggroupconsisting of methyL'ethylland halogen, andv Z stands-lfonaimember of the group 2 .=;A, process. for the manufacture wherein X stands foria member of the group consisting of methyl and'e'thyI, Y stands for a member of thegroup-consisting 'of' methylfethyl and halogen, and'Z stands fori-amember of the group consisting of hydrogen and methyl. v3. A" process for the ma'nufacture' of anthraquinone dyestuffs, comprising condensing anthraquinone compounds containingin an a-position at least one member of the group consisting of halogen, nitro, alkoxyand hydroxy, in presence so I quinone dyestuffs, comprising condensing an- 7 V of a solvent and a diluting agent and copper as catalyst, with an aromatic amine of the genera1+f0rmu1a I1 I NEB I wherein-X stand s for- 'a member ofthe group consisting zofgmethyl; and ethyl; Y stands for a member ofthejgronp consisting,v of methyl, ethyl and ha'loge'n, and Z stands for a member of the group consisting of hydrogen and methyl. 4 g

4. A process for the manufacture of anthrathraquinone compounds containing in an 'm-po-.

sition at least one member of the group consisting of halogen, nitro, alkoxy and hydroxy, in presence. of a solvent and a diluting agent of copper as catalyst and of an acid-binding agent,

' at a temperature between 50 and 250 C.,-with the general formula an aromatic amine of V lfH:

of anthrawherein representsa member of thegroup consistin'g' of hydrogen, halogen, a mino and methylwherein X stands for a memberof the group con sisting of methyl and ethyl, .Y stands for a member of the group consisting of methyl, ethyl and halogen, and Z stands fora member-of the group consisting of hydrogenandl methyl. e 5. A process forj'the;manufacture :of anthraphonated ,anthraquinone compounds containing at least one halogen atom in an a-position with an aromatic ,amine of the general formula:

I wherein Xstands for a member of the group consisting of methyl'andiethyl, Y stands for a memberof the groupiconsisting of methyl, ethylxand halogen, and Z stands for a member ofthe group consisting of hydrogen and methyl, andiperform ingthe condensation in presence of a solventanda diluting agent, of copper as catalyst and of an acid-binding agent at a temperature of 50 to 6. A process forthe manufacture of anthraquin0ne.;d'yestuffs, comprising condensing an anthraquinoneaderivativeof thelgeneral formula amino; B"re'pres entshalogen,"C represents' a member of the group consisting of hydrogen, halogen, alkyl and-sulpho, and D represents a member of the, group-consisting of hydrogen;

halogenand a sulpho groupfwith an aromatic; Y

"amine of the general formula consisting",of methyl andfethyl, .3; stands for a,

member birthgroup "consisting of methyl, ethyl and halogen,and Z stands for a member of the 6 II I 0 halogen wherein R represents a member of the group consisting of hydrogen and methyl and D represents a member of the group consisting of hydrogen,

wherein X stands for a member of the grou 1 halogen, and-'sulphonio acid group with an aro maticamine of the general formula wherein X stands for' a member of the group consisting of methyl and 'ethyL Y stands for a member of the group consisting of methyl, ethyl and halogen, and Z stands for a member of the group consisting of hydrogen and methyl and performing the condensation in presence of a solvent and a diluting agent, of copper as catalyst and of an acid-binding agent at a temperature of 50 to 250 C. V V

8.'A. process for the manufacture ofan'janthraquinone dyestuff, comprising condensing l-amino-Z-sulpho'-4-bromo anthraquinone with l-amino-Z/LG-trlmethylbenzene' in presence of i a solvent and a diluting agent, of copper as catalyst and of an acid-binding agent at a temperature of 50 to 110 C. V i

9. A process for the manufacture" of an anthra quinone dyestufi, comprising condensing l-ami I no-2-sulpho-4 bromo-anthraquinone' with' I'- amino-2,6-dimethylbenzene V in presence of a so-lvent and a diluting'agent, of copper vas'a catalyst.

and'of an acid-binding agent at a temperature of 50 to 110 C.

10. A process for the manufacture of an an-' thraquinone dyestufi, comprising condensing 1amino-2-sulpho-l-bromo-anthraquinone With 1-amino-2-ethyl-4,6-dimethylbenzene in presence of a solvent and a diluting agent, of copper as a catalyst and of an acid-binding agent at a temperature of 50 to 110C.

11. The anthraquin'one dyestufis containingini an u-position at least once in their molecule the grouping e r X 7 wherein X stands for a member of the group consisting of methyl andethyl, Y stands for a member of the group consisting of methyl, ethyl V 12. The anthraquinone dyesmirs of the gefieraliformu la: 1 V I i o= IFH-R' wherein R represents a member of the group consisting of hydrogen and methyl, D represents a member of the group consisting of hydrogen,

halogen; an'd 'sulpho, X represents a" member of the groupconsistingof methyl: and ethyL' Y representsa member of the' group consisting: of

methyl, ethyl and halogen, Z represents a member of the group consisting of hydrogen andmethyl, and V represents a member of the group consisting of hydrogen and sulpho,'said' dyestufis being in: dry state: dark powders, soluble in water with bluedoloratibri and dyeing" animal fibres blue shades. v I i 13. The anthra'q'uinone dyestuff of the 'formula:

l4. 'Iheanthraoujnone dyestuff of' the iormula i NHs.

15. The anthraquinone dyestufi of the-formula g LBiNPETER; 

